化工园区生化出水氯代烃污染物的臭氧氧化降解

以化工园区污水处理厂生化出水为背景水样,考察了臭氧氧化对2,4,6-三氯酚、氯苯、1,2-二氯苯、对硝基氯苯、四氯酞酸5种特征氯代烃污染物的降解效果,并对其降解动力学进行了分析。实验结果表明:臭氧对2,4,6-三氯酚和氯苯的降解效果最好,反应30 min时的去除率均接近100%,其次为1,2-二氯苯和对硝基氯苯,反应30 min时的去除率分别为95.7%和36.0%,最差为四氯酞酸,反应30 min时的去除率仅为8.9%;臭氧对2,4,6-三氯酚和对硝基氯苯的降解符合零级动力学方程,对氯苯和1,2-二氯苯的降解符合一级动力学方程,对四氯酞酸的降解符合二级动力学方程。     

PbO_2复合电极预处理甲苯二胺废水

通过涂覆—热分解法与电沉积法制备了β-PbO_2/α-PbO_2/SnO_2-Sb2O3/Ti复合电极(PbO_2复合电极),采用X射线衍射(XRD)、扫描电子显微镜(SEM)、循环伏安法(CV)、线性极化法(LSV)和加速寿命试验对电极进行表征。将PbO_2复合电极用于处理甲苯二胺(TDA)废水,考察了电解质浓度、电流密度对TDA降解效果的影响。实验结果表明:α-PbO_2呈梭状,β-PbO_2呈花菜状,多层结构的PbO_2电极利于提高电极的稳定性和活性;PbO_2复合电极的析氧电位(1.9 V)明显高于TDA的氧化电位(1.28 V),其使用寿命长达486 d;在电流密度为60 m A/cm2、Na2SO4质量浓度为10 g/L、电解时间为240 min的条件下,对COD为4 791.74 mg/L、TDA质量浓度为486.4mg/L的废水进行处理,TDA去除率高达97.3%,COD去除率可达88.1%。     

臭氧氧化法降解聚氯乙烯离心母液废水中3种有机物

以聚氯乙烯离心母液废水中含量较高的3种有机物(聚乙烯醇、异辛醇和α-甲基苯乙烯)作为目标物,考察臭氧氧化工艺对3种有机物的去除效果,同时考察反应时间、臭氧投加量和初始pH对处理效果的影响。实验结果表明,臭氧氧化处理3种废水的最佳反应时间和臭氧投加量分别为:聚乙烯醇25 min,136 mg/L;异辛醇60min,312 mg/L;α-甲基苯乙烯60 min,32 mg/L。在此条件下,3种有机物的去除率分别为98%、85%和95%。此外,碱性条件有助于臭氧氧化工艺对3种有机物的降解。产物分析结果表明,经臭氧氧化,聚乙烯醇断链后进一步反应生成了草酸单乙酯,异辛醇和α-甲基苯乙烯分别生成了和苯乙酮。     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

催化湿式氧化法处理印染废水的研究

Cu-Fe和Cu-Ce/FSC是优化制备的均相和非均相催化剂,实验中将其应用于实际印染废水的CWAO法处理,考察催化剂的实用性能以及CWAO法对实际印染废水的处理效果。研究结果表明,CWAO法处理印染废水,出水COD、BOD₅均达到三级标准,色度和pH均达到一级标准,非均相的Cu溶出浓度达到三级标准;而处理出水BOD₅/COD由0.021（处理前）提高到0.423（均相）和0.307（非均相）,出水可生化性良好。     

微曝气Fenton氧化法处理模拟双酚A废水的效果及其生物验证

研究了微曝气Fenton氧化法关键工艺参数对模拟双酚A（BPA）废水处理效果的影响,并从活性污泥性质和污染物去除率两方面,采用膜生物反应器(membrane bioreactor, MBR)对微曝气Fenton氧化法的处理效果进行了实验验证,为实现BPA废水的生物处理奠定基础。结果表明,初始pH值、反应时间、H₂O₂/COD(质量浓度比)、H₂O₂/Fe²⁺ (摩尔浓度比)、反应温度及曝气量均对预处理效果有较大影响,在最佳条件下,COD去除率可达70%,BOD/COD值则由原废水的0.02提高到0.50以上。MBR处理上述出水的结果表明,经微曝气Fenton氧化处理BPA的废水,可较好地适应后续的生化处理。     

对苯二甲酸生产废水回用实验研究

采用高级氧化工艺对对苯二甲酸生产废水进行处理,系统考察了氧化剂投加量、废水pH等对处理效果的影响,得出了最佳工艺条件。经过处理的PTA废水,水质达到了车间用水的要求。本方法具有处理效果好、操作简单和环境友好等优点。     

含中间层的DSA电极电催化氧化硝基苯废水的研究

为了提高难降解有机废水的可生化性,以及更高效地去除废水中的特征污染物,同时避免二次污染,利用自制的含锡锑中间层的钌钯氧化物涂层电极对有机废水中的硝基苯进行处理,并利用SEM、XRD等方法对电极中间层、表层进行微观表征。微观测试表明,基体、中间层、表层之间结合力较强,有利于增强电极寿命;水处理实验表明,电催化氧化反应体系适合高浓度有机废水的处理,由于该反应体系需要外加电解质加强传质,这在实际运用中为废水中盐度的处理提供了一种新的途径,当电流密度为20 mA/cm²、电解质浓度为10 g/L、pH=5、极板间距=2 cm时,电催化氧化体系对硝基苯具有较高的去除效率。     

基于超临界水氧化过程的能源环境系统设计

阐述了超临界水氧化过程的工艺路线,介绍了超临界水氧化过程的特点,提出了基于超临界水氧化过程的能源环境系统,设计了几种热量与能量回收系统程的耦合工艺,为提高超临界水氧化过程的经济性奠定了基础。     

Anaerobic ammonium oxidation by Nitrosomonas spp. and anammox bacteria in a sequencing batch reactor

A sequencing batch reactor (SBR) was inoculated with mixed nitrifying bacteria from an anoxic tank at the conventional activated sludge wastewater treatment plant in Nongkhaem, Bangkok, Thailand. This enriched nitrifying culture was maintained under anaerobic conditions using ammonium (NH(4)(+)) as an electron donor and nitrite (NO(2)(-)) as an electron acceptor. Autotrophic ammonium oxidizing bacteria survived under these conditions. The enrichment period for anammox culture was over 100 days. Both ammonium and nitrite conversion rates were proportional to the biomass of ammonium oxidizing bacteria; rates were 0.08 g N/gV SS/d and 0.05 g N/g VSS/d for ammonium and nitrite, respectively, in a culture maintained for 3 months at 42 mg N/L ammonium. The nitrogen transformation rate at a ratio of NH(4)(+)-N to NO(2)(-)-N of 1:1.38 was faster, and effluent nitrogen levels were lower, than at ratios of 1:0.671, 1:2.18, and 1:3.05. Fluorescent in situ hybridization (FISH) was used to identify specific autotrophic ammonium oxidizing bacteria (Nitrosomonas spp., Candidatus Brocadia anammoxidans, and Candidatus Kuenenia stuttgartiensis). The ammonium oxidizing culture maintained at 42 mg N/L ammonium was enriched for Nitrosomonas spp. (30%) over Candidati B. anammoxidans and K. stuttgartiensis (2.1%) while the culture maintained at 210 mg N/L ammonium was dominated by Candidati B. anammoxidans and K. stuttgartiensis (85.6%). The specific nitrogen removal rate of anammox bacteria (0.6 g N/g anammox VSS/d) was significantly higher than that of ammonium oxidizing bacteria (0.4 g N/g Nitrosomonas VSS/d). Anammox bacteria removed up to 979 mg N/L/d of total nitrogen (ammonium:nitrite concentrations, 397:582 mg N/L). These results suggest significant promise of this approach for application to wastewater with high nitrogen but low carbon content, such as that found in Bangkok.